Sulzer Fractional Crystallization
Sulzer Fractional Crystallization
Sulzer Fractional Crystallization
Fractional Crystallization
Fractional Crystallization
Temperature
a
tures to be split into narrow fractions, ultimately leading to top purities of selected A se
para B sep
components, through the virtue of selectivity found in solid liquid equilibria. Frac- tes B solid + melt
A solid
tional crystallization is most frequently encountered in the separation of organic + melt
materials ranging from isomer separations to tar chemical mixtures and from A + B solid
organic acids to monomers. A Eutectic composition B
50
phase is covered by impure mother 40
crystal habit. On the other hand, the liquor which should be removed in or-
Feed
30
absence of a solvent involves smaller der to secure purity. For this reason 20
equipment volumes and does not re- the removal of residual mother liquor 0 10
10 0
quire additional equipment to recover
C B (% )
40
100
plants and in the laboratory. 50
80
90
50
Solid liquid phase equilibria are shown solvent. The feedstock is heated until 80 40 NCB
C oncen
30 p-
tion
90
20
in phase diagrams and classified as molten, and the melt is then cooled un- 100
0
10
cen
tra
eutectic or solid solutions. In multi- til partially frozen. Figure 3 shows how o - NCB C on
component systems many combina- the para isomer can be crystallized out Figure 3: Phase diagram of
tions of eutectic and solid solution be- of a molten mixture of nitrochloroben- Nitrochlorobenzene. Separation of the para
haviour are known. In the absence of zene isomers. isomer is shown.
2
Crystallization Techniques
Figure 4: Figure 5:
Suspension crystallization. Individual crystals Layer Crystallization. Crystal mass is frozen
are freely suspended in liquid. Crystallization onto the cooling surface. Crystallization
proceeds by cooling the liquid. proceeds by cooling the crystal mass.
3
Falling Film Crystallization
Phase 1: Crystallization
A crystalline layer is grown from a falling film of melt on the inside of a tube
which is cooled externally by a cocurrent falling film of a HTM.
Phase 3: Melting
The remaining crystal layer is molten and collected as (intermediate) product.
4
During the third phase, the remaining Feed
solid layer is melted into the collecting
vessel and then transferred to the pro-
duct storage or, in multistage opera-
tion, used for the subsequent purifica-
Product
tion step.
Figure 9:
Small capacity plant (10 tons/year). Fully
automated plant to produce high purity
hydrazine used as propellant for satellites.
The plant has been built for the European
Space Agency. 0691 2804
5
The Falling Film Crystallizer
Phase 1
Phase 2
Phase 3
Time
Figure 12:
Temperature-time profile of the Falling Film
Stage 1 Stage 2 Stage 3 Crystallization.
6
0690 2814-3
Figure 13:
Installation of a crystallizer in an existing
plant.
Figure 14:
0696 2803 Acrylic Acid plant at BASF Antwerpen.
7
Static Crystallization
Melt inlet
Collector
Melt outlet
8
Figure 17:
Paraffin plant at SCHÜMANN SASOL, Germany (100´000 tons/year).
Type 1 2 3 4 5 6 7 8 9
Lenght* mm 1‘910 2‘910 4‘210 4‘910 4‘910 8‘060 8‘060 9‘460 9‘460
Width* mm 1‘020 1‘160 1‘510 1‘710 2‘700 2‘400 3‘090 3‘130 3‘640
Height* mm 3‘570 3‘570 3‘570 3‘570 3‘570 3‘570 3‘570 3‘570 3‘570
Weight (empty) kg 3‘200 5‘600 10‘300 13‘500 21‘000 30‘500 39‘000 46‘000 54‘000
Heat transfer
liquid flow rate m3/h 16 35 70 95 165 240 315 380 450
9
Crystallization with Heat Pump Technology
Refrigerant Refrigerant
separator separator
Compressor Refrigerant Compressor Refrigerant
pump pump
Aux. Aux.
Aux. Cond. Evap. Aux. Cond. Evap.
20
Case 1:
19-24% Prepurification 90-99% Fractional 99.7-99.9%+ 10
mixed p-Xylol
p-X Section p-X Crystallization p-X
Prepurification 0
Temperature ( oC)
Case 2: -10
Separation Co- 19-23% Prepurification 99-99.5% Fractional 99.7-99.9%+
lumns Section Crystallization -20
p-X p-X p-X
-30
Benzol
Case 3:
80-90% 99.7-99.9%+ -40
Toluene Toluene Dispropor- Separation Fractional
tionation Columns p-X Crystallization p-X -50
100 90 80 70 60 50 40 30 20 10 0
Benzene p -Xylene (%)
Figure 19: Flow diagrams of 3 different cases.. Figure 20: Phase diagram of p-Xylene.
10
Heat Pump Crystallizers In order to switch cooling/heating mode Low Energy and Investment Costs
The key equipment of the process are at the end of the crystallization or mel- The heat pump concept improves p-
the heat pump crystallizers. Depen- ting, the feeding of liquid refrigerant Xylene crystallization significantly:
ding on the plant capacity two or more and vapour to the crystallizers is stop-
1. Energy costs are reduced due to
crystallizers of equal size are used ped. Remaining refrigerant is drained
the use of condensation enthalpy
per plant. These crystallizers are inte- into the receiver. The process is then
for crystal melting. And evaporati-
grated in the heat pump refrigeration continued by heating the crystallizer
on energy is higher due to direct
cycle. The crystallizers are designed to containing the crystals and by cooling
cooling inside of the crystallizer
allow switching between cooling with the other crystallizer to start with a new
tubes.
liquid refrigerant and heating with re- crystallization stage.
2. A minimum of equipment is re-
frigerant vapour. Whilst one crystallizer The compressor for the plant operates
quired since process energy is di-
operates in the crystallization mode as in a defined pressure range. When the
rectly used within the crystallizer.
an evaporator, the other one operates pressure exceeds the upper or lower
Refrigeration unit is only equipped
in the sweating or melting mode as a set point vapour is condensed or liquid
with auxiliary heat exchangers to
condenser. evaporated in an auxiliary condenser
eliminate excess energy and to fa-
The heat pump crystallizer basically and evaporator.
cilitate start-up.
consists of a system of vertical ele-
ments used as heat transfer surface.
The isomer mixture enters at the top
of the elementes. Distributors put the
liquid in a falling film flow to the outside
surface of the tubes. The refrigerant for
cooling is distributed at the top through
an internal tube to wet the inside of the
crystallizer tubes.
Refrigeration
Liquid refrigerant is pumped from the
receiver to one crystallizer and is distri-
buted inside the crystallizer tubes. The
temperature level within the crystallizer
is controlled by a valve controling the
evaporation pressure. The low pres-
sure vapour flows then via the recei-
ver to the compressor. The vapour is
compressed to a point where it can be
condensed in the other crystallizer, to
sweat or melt the crystals. The con-
densed refrig-erant flows from the cry-
stallizer via a float valve, back to the
receiver. The refrigeration cycle is thus
completed.
Figure 21:
p-Xylene plant of
CESPA in Spain. 0698 2804-1
11
Combinations to Enhance Performance
Residue
Product
Static
Crystallization
0699 2805
Figure 22: Flow diagram of a plant combining falling film and static crystallization. Figure 24: Acrylic Acid plant at BASF,
Germany
Distillation Crystallization
Isomer
Mixture
Para-
Isomer
Ortho Isomer
Distillation
Crystallization
0699 2801-3
Figure 23: Flow diagram of a plant combining distillation and crystallization.
12
0699 2804 0694 2816-6
Figure 26: Bisphenol A plant at Abbildung 28: Naphthalene plant a Jining, P. R China.
General Electric Plastics, Spain. (10´000 tons/years)
Figure 27:
Naphthalene plant
at Cindu Chemicals
in the Netherlands
(12´000 tons/year).
Figure 29:
Acrylic Acid plant at LG
Chemical, Korea
0693 2804 (20´000 tons/year). 0699 2802
13
Fractional Crystallization
p – cresol
O
benzoic acid
H H
N N
N H C H3
H H
H
hydrazine
O caprolactam
H C C CI
C H3
OH
CI
monochloro HO C OH
dichloro-
acetic acid
benzene
C H3
bisphenol A
H H
CI O
CI
H C C C
n
OH
H H H H
O
fatty acid
C C C
OH naphthalene
H C H3
nitrochlorobenzene
acrylic acid N O2
p-Xylene
test facilities.
General Characteristics of Crystal- – low operating temperatures due to – separation of mixtures forming
lization the nature of phase equilibria azeotropes
– high selectivities due to regularity – reduced thermal degradation due – can replace chemical separation
of the crystal lattice to lower operating temperatures methods
– high purities due to high selectivi- – energy savings due to lower heats
ties of melting, lower operating tempe-
– reduced number of stages due to ratures and reduced number of sta-
high selectivities ges
14
Characteristics of Sulzer Chemtech Crystallization Systems
15
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